Trifluoroacetolysis is a recently-developed method that releases oligosaccharides intact from glycoproteins and glycolipids. Carbohydrate chains released as a mixture from whole tissues, tissue fractions, or cells grown in culture, are easily recovered in nearly quantitative yield and reconstituted to their native form. Analysis of the majority of oligosaccharides containing six or fewer monosaccharide units is performed by combined gas chromatography and mass spectrometry of permethylated, N-trifluoroacetylated oligosaccharide derivatives. Analysis for certain specific oligosaccharides is carried out by radioimmunoassay using antibodies produced against purified oligosaccharides coupled to polypeptide carriers. It is anticipated that the repertoire of oligosaccharide chains produced by cells or tissues will reflect states of cellular differentiation and reveal potential cell surface markers.